WO2012117944A1 - Composition d'encre, procédé de formation d'image et matière imprimée - Google Patents

Composition d'encre, procédé de formation d'image et matière imprimée Download PDF

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Publication number
WO2012117944A1
WO2012117944A1 PCT/JP2012/054449 JP2012054449W WO2012117944A1 WO 2012117944 A1 WO2012117944 A1 WO 2012117944A1 JP 2012054449 W JP2012054449 W JP 2012054449W WO 2012117944 A1 WO2012117944 A1 WO 2012117944A1
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Prior art keywords
group
ink composition
component
composition according
formula
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PCT/JP2012/054449
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English (en)
Japanese (ja)
Inventor
坂本　敦
和公 横井
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富士フイルム株式会社
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Priority claimed from JP2011041819A external-priority patent/JP5819616B2/ja
Priority claimed from JP2011042199A external-priority patent/JP2012180389A/ja
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to EP12752941.0A priority Critical patent/EP2682438B1/fr
Priority to CN2012800101976A priority patent/CN103391979A/zh
Priority to EP16188910.0A priority patent/EP3124557B1/fr
Publication of WO2012117944A1 publication Critical patent/WO2012117944A1/fr
Priority to US14/010,300 priority patent/US10407582B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks

Definitions

  • the present invention relates to an ink composition, an image forming method, and a printed matter.
  • an image recording method for forming an image on a recording medium such as paper based on an image data signal there are an electrophotographic method, a sublimation type and melt type thermal transfer method, an ink jet method and the like.
  • the ink jet method can be implemented with an inexpensive apparatus, and the ink can be efficiently used because the image is directly formed on the recording medium by ejecting the ink only to the required image portion. Running cost is low.
  • the ink jet methods there is a recording method using an ink for ink jet recording that can be cured by irradiation with active energy rays. According to this method, by curing the ink droplets, the productivity of printing can be improved and a sharp image can be formed. It is also possible to mold a printed material on which an image is formed by such an ink jet method.
  • JP-A-2004-339480 discloses a radiation curable ink composition containing an initiator and a polyhedral oligomeric silsesquioxane from the viewpoint of improving curability and sensitivity.
  • Japanese Patent Application Laid-Open No. 2010-13514 discloses an optical nanoparticle containing a polymerization initiator, a polymerizable compound, and a silsesquioxane for the purpose of improving imprintability after heating and curing, substrate adhesion, heat resistance, and surface hardness.
  • a printing composition is disclosed.
  • the first aspect of the present invention has been made in view of the above, and provides an ink composition excellent in moldability and punching characteristics of an image obtained, an image forming method using the same, and a printed matter.
  • the purpose is to achieve the purpose.
  • the second aspect of the present invention has been made in view of the above, an ink composition having good storage stability, excellent punching characteristics and stretchability of an image obtained, an image forming method using the same, and It is an object to provide a printed matter and to achieve the object.
  • Means for solving the problems according to the first aspect are as follows.
  • Component A Ink composition containing a polymer having a group containing a silsesquioxane structure and having a weight average molecular weight of 3,000 or more,
  • Component B a monofunctional polymerizable compound and
  • Component C a polymerization initiator object.
  • the silsesquioxane structure includes a structure represented by the following formula (A-1).
  • R x represents a halogen atom, a cyano group, —SH group, —PR a 2 (R a is an aryl group), an amino group, an aryl group or an alkyl group, and R y is —COO.
  • ⁇ 4> The ink composition according to any one of ⁇ 1> to ⁇ 3>, wherein the silsesquioxane structure is a cage structure.
  • (Component A) has a group containing a silsesquioxane structure in a side chain.
  • (Component A) has a group containing a silsesquioxane structure in a side chain.
  • the group containing a silsesquioxane structure in (Component A) is a group structure represented by the following formula (A-2): Composition.
  • R x represents a halogen atom, a cyano group, —SH group, —PR a 2 (R a is an aryl group), an amino group, an aryl group or an alkyl group, and R y is —COO.
  • a plurality of R x and R y may be the same or different from each other. * Represents a bonding position.
  • ⁇ 13> The ink composition according to any one of ⁇ 1> to ⁇ 12>, which is for inkjet recording.
  • ⁇ 14> an ink application step of applying the ink composition according to any one of ⁇ 1> to ⁇ 13> onto a recording medium; An irradiation step of irradiating the applied ink composition with active energy rays.
  • ⁇ 15> The image forming method according to ⁇ 14>, wherein the ink application step is a step of applying an ink composition by an inkjet method.
  • ⁇ 16> A printed matter formed using the image forming method according to ⁇ 14> or ⁇ 15>.
  • Means for solving the problems according to the second aspect are as follows. ⁇ 17> (Component A ′) a compound having no ethylenically unsaturated double bond and having a silsesquioxane structure and having a molecular weight of 300 or more and less than 3000, (Component B ′) a monofunctional polymerizable compound, (Component C) An ink composition comprising a polymerization initiator and (Component D) a colorant, wherein the content of the (Component B ′) monofunctional polymerizable compound relative to the total content of all polymerizable compounds is 80% by mass or more.
  • R x1 is a halogen atom, a cyano group, a thiol group, —PR a1 2 (R a1 is an aryl group), —SiR c 3 (R c is an alkyl group), an amino group, an aryl group Or R y1 represents a single bond, —COO—, an alkylene group, an arylene group, an alkyleneoxy group, —SO 2 —, —O—, —SiR b1 2 — (R b1 is an alkyl group) or —NH -Represents a group, * represents a bonding position)
  • R x1 is a thiol group, —PR a1 2 (R a1 is an aryl group), —SiR c 3 (R c is an alkyl group), an alkyl group or an aryl group, and R y1
  • R x1 in the structural formula (A) is an aryl group or an alkyl group
  • R y1 is a single bond.
  • R x1 is a halogen atom, a cyano group, a thiol group, -PR a1 2 (R a1 is an aryl group), - SiR c 3 (R c is an alkyl group), an amino group Represents an aryl group or an alkyl group, and R y1 represents a single bond, —COO—, an alkylene group, an arylene group, an alkyleneoxy group, —SO 2 —, —O—, —SiR b1 2 — (R b1 represents an alkyl group) Or a —NH— group, wherein a plurality of R x1 and R y1 may be the same or different from each other.
  • m2 represents an integer of 1 to 5
  • Q 1 represents a single bond, an alkyleneoxy group or an alkylene group.
  • Q 2 represents a hydrogen atom, an alkyl group, an aryl group, an amino group, a hydroxyl group, a sulfo group or an acyl group.
  • Q 3 represents a hydrogen atom or an alkyl group. Q 2 and Q 3 may be bonded to each other to form a ring.
  • R m represents a hydrogen atom or a methyl group.
  • ⁇ 27> The ink composition according to any one of ⁇ 17> to ⁇ 26>, comprising 80 to 99% by mass of (Component B ′) monofunctional polymerizable compound based on the total amount of the ink composition.
  • ⁇ 28> The ink composition according to any one of ⁇ 17> to ⁇ 27>, comprising 0.1 to 20% by mass of the compound (component A ′) with respect to the total amount of the ink composition.
  • ⁇ 29> The ink composition according to any one of ⁇ 17> to ⁇ 28>, which is for inkjet recording.
  • ⁇ 30> an ink application step of applying the ink composition according to any one of ⁇ 17> to ⁇ 29> onto a recording medium; And an irradiation step of irradiating the ink composition with active energy rays.
  • the ink application step is a step of applying the ink composition by an inkjet method.
  • an ink composition excellent in moldability and punching characteristics of an image obtained by curing, an image forming method using the ink composition, and a printed matter According to the second aspect of the present invention, an ink composition having good storage stability can be provided, and an ink composition having excellent punching characteristics and stretchability can be provided.
  • FIG. 3 is a schematic perspective view of a wooden pattern placed in a vacuum forming apparatus in a vacuum forming test for printed matter.
  • the ink composition according to the first aspect of the present invention includes (Component A) a polymer having a group containing a silsesquioxane structure and a weight average molecular weight of 3,000 or more, and (Component B) a monofunctional polymerizable compound. And (Component C) a polymerization initiator.
  • the ink composition of the present invention is preferably for inkjet recording.
  • (Component A) a polymer having a group containing a silsesquioxane structure and having a weight average molecular weight of 3,000 or more
  • (Component B) a monofunctional polymerizable compound
  • (Component C) a polymerization initiator
  • the ink composition according to the second aspect of the present invention comprises (Component A ′) a compound having no ethylenically unsaturated double bond and having a silsesquioxane structure and having a molecular weight of 300 or more and less than 3000, (Component B ′ ) A monofunctional polymerizable compound, (component C) a polymerization initiator, and (component D) a colorant, and the content of (component B ′) monofunctional polymerizable compound relative to the total content of all polymerizable compounds is 80% by mass. It is the above. Hereinafter, it is also simply referred to as “(component A ′)” and “(component B ′)”.
  • the ink composition in the second aspect of the present invention is preferably for inkjet recording.
  • the ink composition in the present invention will be described in detail.
  • the ink composition according to the first aspect of the present invention contains (Component A) a polymer having a group containing a silsesquioxane structure and having a weight average molecular weight of 3,000 or more as an essential component.
  • the silsesquioxane structure in the first aspect of the present invention refers to a siloxane compound formed by the structure of Si (O 1/2 ) 3 having a substituent.
  • a silsesquioxane structure having any structure such as a cage type, a ladder type, or a random type may be used, and a cage-type silsesquioxane structure is more preferable.
  • the "cage type”, “ladder type”, and “random type” refer to structures described in, for example, the chemistry and application development of silsesquioxane materials (CMC Publishing).
  • the silsesquioxane structure in (Component A) preferably includes, for example, a structure represented by the following formula (A-1).
  • R x represents a halogen atom, a cyano group, —SH group, —PR a 2 (R a is an aryl group), an amino group, an aryl group or an alkyl group, and R y is —COO.
  • R x in formula (A-1) is a halogen atom
  • examples of the halogen atom include F, Cl, Br, and I.
  • R y is not a single bond, —COO—, —NH—, or —SO 2 —.
  • the R a when (A-1) in the R x is (are R a aryl group) -PR a 2 is preferably an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms Is more preferable, and an aryl group having 6 to 10 carbon atoms is particularly preferable. Specific examples of the aryl group include a phenyl group and a naphthyl group.
  • R x in Formula (A-1) is —PR a 2 (R a is an aryl group)
  • R y is not a single bond, —COO—, —NH—, or —SO 2 —. .
  • R x in formula (A-1) is an amino group
  • the amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group.
  • R 1 is a substituent
  • the substituents represented by R 1 of the amino group may be different from each other, for example, a linear or branched alkyl group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms), or having 6 to 20 carbon atoms.
  • Examples include an aryl group (preferably a phenyl group).
  • Specific examples of the amino group include a primary amino group and a dimethylamino group.
  • R x in Formula (A-1) is an amino group
  • R y is not a combination of a single bond, —COO— or —NH—, or —SO 2 —.
  • R x in formula (A-1) is an aryl group
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, Ten aryl groups are particularly preferred. Specific examples of the aryl group include a phenyl group and a naphthyl group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R x in the formula (A-1) is an aryl group, R y cannot be —COO—, —NH—, or —SO 2 —.
  • R x in formula (A-1) is an alkyl group
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and 1 to The alkyl group of 3 is particularly preferred.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure, but preferably has a cyclic structure or a branched structure.
  • An epoxy group may be contained in the chain or cyclic alkyl group.
  • two carbons which form an epoxy group when including an epoxy group shall be included in the number of carbon atoms described above.
  • alkyl group examples include 1,2-epoxy-4-cyclohexyl group, glycidyl group, isobornyl group, methyl group, ethyl group, t-butyl group, isooctyl group and the like. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R x in formula (A-1) is a —SH group
  • R y is not a single bond, —COO— or —NH— combination.
  • R x in formula (A-1) is preferably an aryl group or an alkyl group.
  • R y in formula (A-1) is an alkylene group
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • Specific examples of the alkylene group include a methylene group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R y in formula (A-1) is an arylene group
  • the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and 6 to 6 carbon atoms. 10 is particularly preferred.
  • Specific examples of the arylene group include a phenylene group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R y in formula (A-1) is an alkyleneoxy group (—R 2 —O—, R 2 is an alkylene group)
  • the alkyleneoxy group preferably has 1 to 10 carbon atoms, 6 is more preferable, and 1 to 3 carbon atoms is particularly preferable.
  • Specific examples of the alkyleneoxy group include an ethoxy group. These groups may or may not have a substituent.
  • the alkyleneoxy group is bonded to Si in the structural formula (A-1) in the direction of ** — R 2 —O— or ** — O—R 2 — (** represents a bonding position). be able to.
  • R y in formula (A-1) is —SiR b 2 — (R b is an alkylene group)
  • R b preferably has 1 to 10 carbons, more preferably 1 to 6 carbons, Numbers 1 to 3 are particularly preferable.
  • Specific examples of the alkylene group include a methylene group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R b when R y in formula (A-1) is —SiR b 2 — (R b is a halogen atom) include F, Cl, Br, I and the like.
  • R y in formula (A-1) is —COO—, an alkylene group, an arylene group, an alkyleneoxy group, —SO 2 —, —SiR b 2 — (R b is an alkylene group or a halogen atom), and —NH—.
  • Groups selected from the group consisting of may be combined. Preferred combinations of groups include a combination of —NH— and an alkylene group, a combination of —COO— and an alkylene group, and the like.
  • R y in formula (A-1) is preferably a single bond or an alkylene group, and particularly preferably a single bond.
  • the group containing a silsesquioxane structure in (Component A) is preferably a group represented by the following formula (A-2).
  • R x represents a halogen atom, a cyano group, —SH group, —PR a 2 (R a is an aryl group), an amino group, an aryl group or an alkyl group, and R y is —COO.
  • a plurality of R x and R y may be the same or different from each other. * Represents a bonding position.
  • R x in formula (A-2) is the same including the definition of R x in formula (A-1) and the preferred range.
  • R y in formula (A-2) is the same including the definition and preferred range of R y in formula (A-1) described above.
  • R x represents an alkyl group or an aryl group and R y represents a single bond is particularly preferable.
  • the weight average molecular weight (Mw) of (Component A) in the first embodiment of the present invention is 3,000 or more, preferably 3,000 to 200,000, more preferably 5,000 to 200,000, 000 to 200,000 is particularly preferred.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC).
  • GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (4.6 mm ID ⁇ 15 cm, Tosoh Corporation) as columns and THF (tetrahydrofuran) as an eluent. Can be used.
  • the content of (Component A) in the ink composition according to the first aspect of the present invention is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and 1% by mass to 10% by mass. Mass% is particularly preferred.
  • Examples of monomers that give a repeating unit having a group containing a cage silsesquioxane structure include, for example, silsesquioxane (completely condensed series) manufactured by Sigma-Aldrich Japan, and silsesquioxane series manufactured by Hybrid Plastic. Etc.
  • each repeating unit forming a known, known or commercially available styrene, (meth) acrylate, (meth) acrylamide, ester, urethane, urea can be used. It preferably has a (meth) acrylate repeating unit or a urethane repeating unit (—NHCOO—), and more preferably has a urethane repeating unit.
  • (Meth) acrylamide” means at least one of acrylamide and methacrylamide, and the notation for adding (meth) to other (meth) acrylates is the same as this.
  • Examples of the monomer capable of forming a styrene repeating unit include styrene and p-methoxystyrene.
  • Examples of the monomer capable of forming the (meth) acrylate repeating unit include methyl (meth) acrylate, ethyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexylglycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyeth I
  • Examples of monomers capable of forming (meth) acrylamide repeating units include (meth) acrylamide, N-butyl (meth) acrylamide, Np-hydroxyphenyl (meth) acrylamide, p-sulfamoylphenyl ( And (meth) acrylamide.
  • Examples of the polyvalent carboxylic acid monomer capable of forming an ester repeating unit include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • diol monomer capable of forming a urethane repeating unit examples include alkylene diol, polyether diol, polyester diol, polycaprolactone diol such as Plaxel series (Placcel 205U) manufactured by Daicel Chemical Industries, and Ube Industries, Ltd.
  • Polycarbonate diols such as ETERNACOLL series (UH, UM series), polypropylene diols such as PPG series (PPG300, PPG700, PPG1000) manufactured by Wako Pure Chemical Industries, Ltd., and the like.
  • diisocyanate monomer capable of forming a urethane repeating unit examples include monomers having the following structure.
  • Component A is an embodiment having (i) a group containing a silsesquioxane structure in the side chain, (ii) an embodiment having a group containing a silsesquioxane structure at the end of the main chain, and (iii) silsesquioxane.
  • the mode which has the group containing a structure in a side chain and the principal chain terminal can be taken.
  • (Component A) is preferably an embodiment having the group containing a silsesquioxane structure in the side chain (the embodiments (i) and (iii)).
  • the main chain structure preferably has a (meth) acrylate repeating unit or a urethane repeating unit (—NHCOO—). More preferably, it has a unit (—NHCOO—).
  • (Component A) has a group containing a silsesquioxane structure in the side chain, it is preferably a structure represented by the following formula (i-1).
  • X a is a residue obtained by removing four hydrogen atoms from a hydrocarbon having 1 to 10 carbon atoms
  • R d represents a hydrogen atom or an alkyl group
  • W a is a single bond or , —O—, —SiR e 2 — (R e is an alkyl group) or at least one group selected from the group consisting of alkylene groups
  • T ′ represents the following formula (A-21).
  • R x represents a halogen atom, a cyano group, —SH group, —PR a 2 (R a is an aryl group), an amino group, an aryl group or an alkyl group, and R y is —COO.
  • a plurality of R x and R y may be the same or different from each other, and * represents a bonding position.
  • X a in the formula (i-1) represents a residue obtained by removing four hydrogen atoms from a hydrocarbon having 1 to 10 carbon atoms.
  • the hydrocarbon having 1 to 10 carbon atoms may have a straight chain structure, a branched structure, or a cyclic structure.
  • the hydrocarbon having 1 to 10 carbon atoms may contain an —O— bond.
  • the hydrocarbon preferably has 2 to 6 carbon atoms, and particularly preferably 3 to 9 carbon atoms. Specific examples include residues obtained by removing two hydrogen atoms from alkanes such as propane, butane, pentane, and cyclohexane.
  • R d in the formula (i-1) represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
  • the alkyl group represented by R d in the formula (i-1) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. The group is particularly preferred.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure, but a linear structure or a cyclic structure is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, and a t-butyl group.
  • W a in the formula (i-1) represents at least one group selected from the group consisting of —O—, —SiR e 2 — (R e is an alkyl group) or an alkylene group, or a single bond, A group in which —SiR e 2 — and —O— are combined, or a single bond is more preferable.
  • the (i-1) in the W -SiR in a e 2 - is (R e is an alkyl group) as R e 2 in, preferably an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms Is more preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure. Specific examples of the alkyl group include a methyl group, an ethyl group, and a t-butyl group.
  • the alkylene group for W a in (i-1) is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms. is there.
  • the alkylene group may be a linear structure, a branched structure, or a cyclic structure, but a cycloalkylene group is preferred. Specifically, it represents a methylene group, a cyclopropylene group, a cyclohexylene group or the like, and a cyclohexylene group is particularly preferable. These groups may or may not have a substituent, but preferably do not have a substituent.
  • W a in the formula (i-1) may be a combination of at least one group selected from the group consisting of —O—, —SiR e 2 — (R e is an alkyl group) or an alkylene group. .
  • the combination of the groups is preferably a combination of —O— and —SiR e 2 —.
  • R x and R y in formula (A-21) are the same including the definition and preferred range of R x and R y in formula (A-2), including the preferred range.
  • Specific examples (i-1-1) to (i-1-3) of the repeating unit represented by the formula (i-1) are listed below, but the present invention is not limited thereto.
  • (Component A) has a group containing a silsesquioxane structure in the side chain and has a repeating unit represented by the formula (i-1), it is represented by the formula (i-1).
  • the ratio of the repeating unit is, for example, preferably 5 to 90% by mass, more preferably 20 to 90% by mass in all the structural units (monomers).
  • (Component A) When (Component A) has a group containing a silsesquioxane structure in the side chain, (Component A) preferably further has a structure represented by the following formula (i-2).
  • R x ′ represents at least one group selected from the group consisting of an alkylene group and an arylene group.
  • the alkylene group represented by R X ′ in formula (i-2) is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably a carbon number. 1-12.
  • the alkylene group may be a linear structure, a branched structure, or a cyclic structure, but a cycloalkylene group is preferred. Specifically, it represents a methylene group, a cyclopropylene group, a cyclohexylene group or the like, and a cyclohexylene group is particularly preferable.
  • the arylene group represented by R x ′ in formula (i-2) is preferably an arylene group having 6 to 15 carbon atoms, and specifically includes a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, and the like. Is mentioned.
  • R x ′ in formula (i-2) may be combined with an alkylene group or an arylene group.
  • a preferred combination of groups is a combination of an alkylene group having 1 to 12 carbon atoms and an arylene group having 6 to 15 carbon atoms. Specific examples include the following groups (i-2-a), (i-2-b), (i-2-c) and the like (* represents a bonding position).
  • R x ′ in formula (i-2) may or may not have a substituent, but preferably does not have a substituent.
  • (Component A) has a group containing a silsesquioxane structure in the side chain and has a repeating unit represented by Formula (i-2), it is represented by Formula (i-2).
  • the proportion of repeating units is, for example, preferably from 10 to 95% by mass, more preferably from 30 to 90% by mass, based on all the structural units (monomers) contained in (Component A).
  • (Component A) has a group containing a silsesquioxane structure in the side chain
  • a known polycondensation reaction such as a chain polymerization reaction or a polycondensation reaction with a monomer having the specific structure described above is performed. It can be synthesized by doing.
  • a monomer having a silsesquioxane structure and having a radical polymerizable group can be synthesized by copolymerizing the polymer and a monomer giving the above-mentioned (meth) acrylate repeating unit.
  • the main chain structure preferably has a (meth) acrylate repeating unit or a urethane repeating unit (—NHCOO—). More preferably, it has a repeating unit (—NHCOO—).
  • (Component A) When (Component A) has a group containing a silsesquioxane structure at the end of the main chain, it may be contained in at least one of the main chain structures, but may be contained at both ends. It is preferably contained at both ends of the structure. Further, the terminal structure may be branched to have a group containing a plurality of silsesquioxane structures. When (Component A) has a group containing a silsesquioxane structure at the end of the main chain, it preferably has a structure represented by the following formula (A-22) at the end of the main chain.
  • R x represents a halogen atom, a cyano group, —SH group, —PR a 2 (R a is an aryl group), an amino group, an aryl group or an alkyl group, and R y is —COO.
  • a plurality of R x and R y may be the same or different from each other, and * represents a bonding position.
  • R x and R y in formula (A-22) are the same including the definitions and preferred ranges of R x and R y in formula (A-2).
  • (Component A) When (Component A) has a group containing a silsesquioxane structure at the end of the main chain, (Component A) preferably further has a structure represented by the following formula (ii-1).
  • R x' is R x'represents at least one group selected from the group consisting of an alkylene group and an arylene group.
  • R x ′ in formula (ii-1) is the same as the definition of R x ′ in formula (i-2), including a preferable range.
  • (Component A) has a group containing a silsesquioxane structure at the end of the main chain and has a repeating unit represented by the formula (ii-1), it is represented by the formula (ii-1).
  • the proportion of the repeating unit is, for example, preferably from 10 to 90% by mass, more preferably from 15 to 80% by mass, based on all the structural units (monomers).
  • a vinyl ether having an active hydrogen group is prepared by a known polycondensation or polyaddition reaction of urethane, (meth) acrylate, ester or the like.
  • a precursor can be synthesized by performing a termination reaction with a compound or the like, and further, a silsesquioxane compound having a thiol group, an amino group, or the like can be further added to the precursor and synthesized.
  • (Component A) When (Component A) has an embodiment having a group containing a silsesquioxane structure at the side chain and at the end of the main chain, it may have a (meth) acrylate repeating unit or a urethane repeating unit (—NHCOO—) as the main chain structure. Preferably, it has a urethane repeating unit (—NHCOO—).
  • the structure that the main chain structure preferably has in the embodiment having (i) the group containing a silsesquioxane structure at the side chain
  • the main chain structure preferably has a group in an embodiment having an acetal bond at the end of the main chain. More specifically, the main chain structure preferably has the structure of formula (i-1) and the main chain terminal structure preferably has a group of formula (A-22).
  • Component A has a group containing a silsesquioxane structure at the side chain and the main chain terminal, (i) the synthesis method of the embodiment having a group containing a silsesquioxane structure in the side chain; and (ii) It can be synthesized by combining the synthesis methods of the embodiment having a group containing a silsesquioxane structure at the end of the main chain.
  • the ink composition of the present invention contains (component A ′) a compound having no ethylenically unsaturated double bond and having a silsesquioxane structure and having a molecular weight of 300 or more and less than 3000 as an essential component.
  • the compound having a silsesquioxane structure in the second aspect of the present invention is not limited as long as it is a siloxane compound formed by the structure of Si (O 1/2 ) 3 having a substituent.
  • a silsesquioxane structure having any structure such as a cage type, a ladder type, or a random type may be used, and a cage-type silsesquioxane structure is more preferable.
  • the "cage type”, "ladder type”, and “random type” refer to structures described in, for example, the chemistry and application development of silsesquioxane materials (CMC Publishing).
  • the silsesquioxane structure in the second aspect of the present invention is preferably a structure represented by the following structural formula (A).
  • R x1 is a halogen atom, a cyano group, a thiol group, —PR a1 2 (R a1 is an aryl group), —SiR c 3 (R c is an alkyl group), an amino group, an aryl group Or R y1 represents a single bond, —COO—, an alkylene group, an arylene group, an alkyleneoxy group, —SO 2 —, —O—, —SiR b1 2 — (R b1 is an alkyl group) or —NH -Represents a group, * represents a bonding position)
  • R x1 in the structural formula (A) is a halogen atom
  • examples of the halogen atom include F, Cl, Br, I and the like.
  • R y1 is not a combination with a single bond, —COO—, —SO 2 — or —NH—.
  • R x1 in the structural formula (A) is -PR a1 2 (R a1 is an aryl group)
  • R a1 is preferably an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 16 carbon atoms Is more preferable, and an aryl group having 6 to 10 carbon atoms is particularly preferable.
  • Specific examples of the aryl group include a phenyl group and a naphthyl group.
  • a plurality of R a1 may be the same or different.
  • R y1 is not a single bond, —COO—, —SO 2 — or —NH—.
  • R c is when R x1 in the structural formula (A) is (R c is an alkyl group) -SiR c 3 is preferably an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 8 carbon atoms Is particularly preferred.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure. Specific examples of the alkyl group include a methyl group.
  • a plurality of R c may be the same or different.
  • R x1 in the structural formula (A) is an amino group
  • the amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.
  • R 3 is a substituent
  • the substituents represented by R 3 of the amino group may be different from each other, for example, a linear or branched alkyl group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms), or having 6 to 20 carbon atoms. Examples include an aryl group (preferably a phenyl group). Specific examples of the amino group include a primary amino group and a dimethylamino group.
  • R x1 is an amino group
  • R y1 is not a combination with a single bond, —COO—, —SO 2 — or —NH—.
  • R x1 in the structural formula (A) is an aryl group
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
  • Aryl groups are particularly preferred. Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R x1 in the structural formula (A) is an alkyl group
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 3 to 8 carbon atoms.
  • the alkyl group is more preferable.
  • the alkyl group may be a linear structure, a branched structure, or a cyclic structure, but is preferably a chain, and particularly preferably a chain alkyl group having 3 to 8 carbon atoms.
  • An epoxy group may be contained in the chain or cyclic alkyl group.
  • two carbons which form an epoxy group when including an epoxy group shall be included in the number of carbon atoms described above.
  • alkyl group examples include a 3,4-epoxy-cyclohexyl group, a glycidyl group, a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a t-butyl group, and the like, and an isobutyl group and an isooctyl group include Particularly preferred.
  • These groups may or may not have a substituent, but preferably do not have a substituent.
  • R x1 in the structural formula (A) is preferably an aryl group, an alkyl group, a thiol group, or an amino group, more preferably an alkyl group or an aryl group, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 3 to 8 carbon atoms.
  • a chain alkyl group is particularly preferred.
  • R y1 in the structural formula (A) is an alkylene group
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • Specific examples of the alkylene group include a methylene group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R y1 in the structural formula (A) is an arylene group
  • the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and 6 to 10 carbon atoms. It is particularly preferred that Specific examples of the arylene group include a phenylene group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R y1 in the structural formula (A) is an alkyleneoxy group (—R 4 —O—, R 4 is an alkylene group)
  • the alkyleneoxy group preferably has 1 to 10 carbon atoms, and 1 to 6 carbon atoms. Are more preferable, and those having 1 to 3 carbon atoms are particularly preferable.
  • Specific examples of the alkyleneoxy group include an ethoxy group. These groups may or may not have a substituent.
  • the alkyleneoxy group is bonded to Si in the structural formula (A) in any direction of ** — R 4 —O— and ** — O—R 4 — (** represents a bonding position). It may be.
  • R y1 in Structural Formula (A) is —SiR b1 2 — (R b1 is an alkyl group)
  • R b1 preferably has 1 to 10 carbons, more preferably 1 to 6 carbons, 1-3 are particularly preferred.
  • Specific examples of the alkyl group include a methyl group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • R y1 in the structural formula (A) is preferably a single bond, an alkylene group or an arylene group, and more preferably a single bond.
  • R x1 is a thiol group, —PR a1 3 group, —SiR c 3 group, alkyl group or aryl group
  • R y1 is an alkylene group, an alkyleneoxy group or a single bond
  • R x1 is an alkyl group or an aryl group
  • a combination in which R y1 is a single bond is particularly preferable.
  • the compound having a silsesquioxane structure represented by the structural formula (A) is preferably a compound represented by the following general formula (A′-1).
  • R x1 -R y1 -SiO 3/2 m1 general formula (A′-1)
  • R x1 is a halogen atom, a cyano group, a thiol group, -PR a1 2
  • R a1 is an aryl group
  • R y1 is a single bond, -COO-, alkylene group, an arylene group, an alkylene group, -SO 2 -, - O - , - SiR b1 2 -.
  • R b1 represents an alkyl group) to represent plurality of or -NH- group
  • R x1 And R y1 may be the same or different from each other, and m1 represents an integer of 6 to 10.
  • R x1 in formula (A'-1) is the same, including defined as the preferred ranges of R x1 in the structural formula of the above (A).
  • R y1 in the general formula (A′-1) is the same including the definition and preferred range of R y1 in the structural formula (A).
  • R x1 is a thiol group, —PR a1 3 group, —SiR c 3 group, an alkyl group or an aryl group
  • R y1 is an alkylene group, an alkyleneoxy group, or a single bond
  • a certain combination is preferable, and a combination in which R x1 is an alkyl group or an aryl group and R y1 is a single bond is particularly preferable.
  • m1 is an integer of 6 to 10, and m1 is preferably 8.
  • m1 8
  • Component A ′ is represented by the structure of the following general formula (A′-2).
  • the compound having a silsesquioxane structure represented by the structural formula (A) is preferably a compound represented by the following general formula (A′-2).
  • R x1 is a halogen atom, a cyano group, a thiol group, -PR a1 2 (R a1 is an aryl group), - SiR c 3 (R c is an alkyl group), an amino group Represents an aryl group or an alkyl group, and R y1 represents a single bond, —COO—, an alkylene group, an arylene group, an alkyleneoxy group, —SO 2 —, —O—, —SiR b1 2 — (R b1 represents an alkyl group) Or a —NH— group, wherein a plurality of R x1 and R y1 may be the same or different from each other.
  • R x1 in the general formula (A′-2) is the same including the definition and preferred range of R x1 in the structural formula (A).
  • R y1 in formula (A'-2) are the same, including defined as the preferred ranges of R y1 in the structural formula of the above (A).
  • R x1 is a thiol group, —PR a1 3 group, —SiR c 3 group, an alkyl group or an aryl group
  • R y1 is an alkylene group, an alkyleneoxy group, or a single bond
  • a certain combination is preferable, and a combination in which R x1 is an alkyl group or an aryl group and R y1 is a single bond is particularly preferable.
  • the content of (Component A ′) with respect to the total amount of the ink composition in the second embodiment of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 5% by mass, and particularly The content is preferably 1 to 5% by mass.
  • Component A ′ in the second embodiment of the present invention has a molecular weight of 300 or more and less than 3000, preferably 300 to 2500, more preferably 600 to 2000, and particularly preferably 800 to 1400.
  • Component A ′ in the second aspect of the present invention is, for example, a known compound such as a silsesquioxane (fully condensed series) manufactured by Sigma-Aldrich Japan, or a silsesquioxane series manufactured by Hybrid Plastic. Can be used. Moreover, a well-known compound can also be suitably synthesize
  • the ink composition according to the first aspect of the present invention contains (Component B) a monofunctional polymerizable compound as an essential component.
  • the monofunctional polymerizable compound used in the ink composition according to the first aspect of the present invention is not limited as long as it is a polymerizable compound having one polymerizable group.
  • the monofunctional polymerizable compound used in the ink composition according to the first aspect of the present invention may be either a radical polymerizable compound or a cationic polymerizable compound, but is preferably a radical polymerizable compound.
  • compounds having an ethylenically unsaturated bond capable of radical polymerization More specifically, any compound having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule may be used.
  • Examples of monofunctional polymerizable compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and unsaturated carboxylic acid esters. And salts thereof; anhydrides having an ethylenically unsaturated group; acrylonitrile; styrene and the like. Further, various macromonomers such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated polyurethanes are also included.
  • Examples of such monofunctional compounds include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate, N- Methylolacrylamide, diacetoneacrylamide, epoxy acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl phthalate Acid, methoxy-polyethylene glycol acrylate, 2-acryloyloxyethyl-2-hydride Xylethylphthalic acid, cyclic trimethylolpropane formal acrylate, 2- (2-ethoxyethoxy) ethyl acrylate,
  • monofunctional vinyl ether compounds include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-octadecyl vinyl ether, 2-ethylhexyl vinyl ether, n -Nonyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, Butoxyethylbi Ether,
  • N-vinyl compounds such as N-vinyl lactams and N-vinylformamide.
  • Preferred examples of N-vinyl lactams are represented by the following formula.
  • m represents an integer of 1 to 5
  • m is preferably an integer of 2 to 4
  • m is more preferably 2 or 4
  • m is 4. That is, N-vinylcaprolactam is particularly preferable.
  • the monofunctional polymerizable compound of the present invention preferably contains an N-vinyl compound or (meth) acrylate.
  • the monofunctional radically polymerizable monomer of the present invention is preferably used in combination.
  • a preferred combination is a combination of an acrylate compound, an N-vinyl compound, and a (meth) acrylamide compound.
  • Examples of the monofunctional polymerizable compound that can be used in the first aspect of the present invention also include a cationic polymerizable compound.
  • a cationic polymerizable compound There is no particular limitation as long as it is a compound that causes a polymerization reaction with an acid generated from a photoacid generator and cures, and various known cationically polymerizable compounds known as photocationically polymerizable compounds can be used.
  • Examples of the cationic polymerizable compound include an epoxy compound and an oxetane compound.
  • Examples of monofunctional epoxy compounds that can be used in the first aspect of the present invention include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1, 2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxy Examples thereof include methylcyclohexene oxide and 3-vinylcyclohexene oxide.
  • the molecular weight of the (component B) monofunctional polymerizable compound is preferably 130 to 3000, and more preferably 130 to 500.
  • Component B monofunctional polymerizable compound relative to the total polymerizable compound (the total content of the monofunctional polymerizable compound and, if necessary, the polyfunctional polymerizable compound) in the ink composition according to the first aspect of the present invention
  • the content of is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and particularly preferably 90 to 100% by mass.
  • the content of the (component B) monofunctional polymerizable compound in the ink composition according to the first embodiment of the present invention is preferably 50% by mass or more, more preferably 50 to 95% by mass, and particularly preferably 60 to 90% by mass. preferable.
  • the ink composition according to the first aspect of the present invention may have a polyfunctional polymerizable compound.
  • the polyfunctional polymerizable compound that can be used in the ink composition according to the first aspect of the present invention is not limited as long as it is a polymerizable compound having two or more polymerizable groups.
  • Polyfunctional compounds capable of radical polymerization include bis (4-acryloxypolyethoxyphenyl) propane, tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipentaerythritol tetraacrylate, trimethylolpropane (PO modified) ) Triacrylate, oligoester acrylate, hydroxypivalate neopentyl glycol diacrylate, tetramethylol methane triacrylate, dimethylol tricyclodecane diacrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A di Acrylates, bisphenol A PO adduct diacrylate, bisphenol A with EO Diacrylate, dipentaerythritol hexaacrylate, propylene glycol diglycidyl ether acrylic acid adduct, ditrimethylolpropane tetraacrylate and other acrylate
  • allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • PO represents propylene oxide
  • EO represents ethylene oxide. More specifically, Shinzo Yamashita, “Cross-linking agent handbook” (1981, Taiseisha); Kato Kiyomi ed., “UV / EB curing handbook (raw material)” (1985, Polymer publication society); Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); written by Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products or radically polymerizable or crosslinkable compounds known in the industry can be used.
  • polyfunctional vinyl ether can be mentioned.
  • the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butylene glycol divinyl ether, butanediol divinyl ether, hexane.
  • Divinyl ethers such as diol divinyl ether, cyclohexane dimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl Ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, Propylene oxide addition ditrimethylolpropane tetra
  • radically polymerizable polyfunctional polymerizable compounds include, for example, JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, and JP-A-9-134011.
  • active energy ray-curable polymerizable compounds used in the photopolymerizable compositions described in JP-A-2004-514014 and other publications are known, and these are also applied to the ink composition of the present invention. be able to.
  • polyfunctional epoxy compounds as cationically polymerizable compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F di Glycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxa Bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyle
  • the molecular weight of the polyfunctional polymerizable compound is preferably 130 to 3000, and more preferably 130 to 500, as the molecular weight.
  • the content of the polyfunctional polymerizable compound in the total polymerizable compound is preferably 0.1% by mass to 50% by mass, The content is more preferably 1 to 20% by mass, and particularly preferably 1 to 5% by mass.
  • the ink composition according to the second aspect of the present invention contains (Component B ′) a monofunctional polymerizable compound as an essential component, and (Component B ′) with respect to the total content of all polymerizable compounds in the ink composition. It is essential that the content of the monofunctional polymerizable compound is 80% by mass or more.
  • the content of the (component B ′) monofunctional polymerizable compound in the total polymerizable compound of the ink composition according to the second aspect of the present invention is 80% by mass or more, preferably 80 to 99% by mass, More preferably, it is 95 to 99% by mass.
  • the total polymerizable compound in the second aspect of the present invention refers to the total content of (Component B ′) monofunctional polymerizable compound and a polyfunctional polymerizable compound (described later) added as necessary.
  • the monofunctional polymerizable compound used in the ink composition according to the second aspect of the present invention is not limited as long as it is a polymerizable compound having one polymerizable group.
  • the monofunctional polymerizable compound used in the ink composition according to the second aspect of the present invention is preferably a radical polymerizable compound, and includes a compound having an ethylenically unsaturated bond capable of radical polymerization. More specifically, any compound having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule may be used.
  • polymerizable monomers having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, unsaturated carboxylic acid esters, and the like.
  • unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, unsaturated carboxylic acid esters, and the like.
  • various macromonomers such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated polyurethanes are also included.
  • Examples of such monofunctional compounds are preferably 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate, epoxy acrylate.
  • monofunctional vinyl ether compounds include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-octadecyl vinyl ether, 2-ethylhexyl vinyl ether, n -Nonyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, Butoxyethylbi Ether,
  • (meth) acrylamide compounds are also preferred.
  • a preferred example of (meth) acrylamide is represented by the following general formula (M′-1).
  • Q 1 represents a single bond, an alkyleneoxy group or an alkylene group.
  • Q 2 represents a hydrogen atom, an alkyl group, an aryl group, an amino group, a hydroxyl group, a sulfo group or an acyl group.
  • Q 3 represents a hydrogen atom or an alkyl group. Q 2 and Q 3 may be bonded to each other to form a ring.
  • R m represents a hydrogen atom or a methyl group.
  • the alkyleneoxy group preferably has 1 to 10 carbon atoms, 1 to 6 is more preferable, and 1 to 3 carbon atoms is particularly preferable.
  • Specific examples of the alkyleneoxy group include an ethoxy group. These groups may or may not have a substituent.
  • the alkyleneoxy group has a Q in the structural formula (M′-1) in any direction of ** — R 5 —O— and ** — O—R 5 — (** represents a bonding position). 2 may be combined.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • Specific examples of the alkylene group include a methylene group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • Q 1 in the general formula (M′-1) is preferably a single bond.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 More preferred are alkyl groups of ⁇ 8.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure. Specific examples of the alkyl group include a methyl group, an ethyl group, an isobutyl group, an isopropyl group, an isooctyl group, a t-butyl group, and a cyclohexyl group. These groups may or may not have a substituent, but preferably have a substituent.
  • Examples of the substituent when the alkyl group represented by Q 2 in formula (M′-1) has a substituent include a hydroxyl group.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, Particularly preferred are 6 to 10 aryl groups.
  • Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable. These groups may or may not have a substituent, but preferably do not have a substituent.
  • the amino group may be any of a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group. , -NH 2 , -NHR 6 , -NR 6 2 , -NH 3 + or -NR 6 3 + (R 6 is a substituent).
  • the substituents represented by R 6 of the amino group may be different from each other.
  • Examples include an aryl group (preferably a phenyl group).
  • Specific examples of the amino group include a primary amino group and a dimethylamino group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • examples of the sulfo group include a sulfo group or a salt of the sulfo group (—SO 3 X, X is an alkali metal salt).
  • examples of the salt of the sulfo group include —SO 3 Li, —SO 3 Na, —SO 3 K and the like, —SO 3 Na is preferred.
  • the acyl group preferably has 1 to 10 carbon atoms, 5 is more preferable, and 1 to 3 carbon atoms are particularly preferable.
  • Specific examples of the acyl group include —COCH 3 and the like.
  • Q 2 in the general formula (M′-1) is preferably an alkyl group, an amino group, or a hydroxyl group.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. More preferred is an alkyl group having 3 to 8 carbon atoms.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure. Specific examples of the alkyl group include a methyl group, an ethyl group, an isobutyl group, an isooctyl group, and a t-butyl group. These groups may or may not have a substituent, but preferably do not have a substituent.
  • Q 3 in formula (M′-1) represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
  • R m in formula (M′-1) represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
  • the ring formed is a ring composed of an atom selected from a carbon atom and an oxygen atom. Is preferred. Specific examples of the ring formed include a pyrrolidine ring, a piperidine ring, an oxazine ring and the like, and an oxazine ring is particularly preferable. These groups may or may not have a substituent, but preferably do not have a substituent.
  • any monofunctional polymerizable compound having a (meth) acrylamide group may be used, and an N-substituted (meth) acrylamide compound may be used. Good.
  • N-isopropylacrylamide, N-tert-butylacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide, N- [3- (dimethylamino) propyl] acrylamide N- (1,1-dimethyl-3-oxobutyl) acrylamide and 4-acryloylmorpholine are more preferable, and N-isopropylacrylamide, N, N-dimethylacrylamide and 4-acryloylmorpholine are particularly preferable.
  • the glass transition temperature is preferably 60 ° C. to 180 ° C., particularly preferably 70 ° C. to 160 ° C.
  • the content of the (meth) acrylamide compound is from 0.1% by mass to the total amount of the ink composition. 75% by mass is preferable, 5% by mass to 50% by mass is more preferable, and 10% by mass to 40% by mass is particularly preferable.
  • N-vinyl compounds such as N-vinyl lactams and N-vinylformamide.
  • Preferred examples of N-vinyl lactams are represented by the following formula.
  • m2 represents an integer of 1 to 5
  • m2 is preferably an integer of 2 to 4, more preferably m2 is 2 or 4, and m2 is 4.
  • Particularly preferred is N-vinylcaprolactam.
  • the content of the N vinyl compound is 0.1% by mass to 50% by mass with respect to the total amount of the ink composition. 5 mass% to 40 mass% is more preferable, and 10 mass% to 35 mass% is particularly preferable.
  • the (component B ′) monofunctional polymerizable compound may contain an N-vinyl compound or a (meth) acrylamide compound from the viewpoint of stretchability of the resulting image and indentation curing sensitivity. It is particularly preferable to contain a (meth) acrylamide compound.
  • the molecular weight of the monofunctional polymerizable compound is preferably 130 to 3000, and more preferably 130 to 500.
  • the ink composition in the second aspect of the present invention may contain a bifunctional or higher polyfunctional polymerizable compound.
  • the radically polymerizable polyfunctional compound that may be included is bis (4-acryloxypolyethoxyphenyl) propane, tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol.
  • allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • PO represents propylene oxide
  • EO represents ethylene oxide. More specifically, Shinzo Yamashita, “Crosslinker Handbook”, (1981 Taiseisha); Kato Kiyosumi, “UV / EB Curing Handbook (Materials)” (1985, Polymer Publications); Radtech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products or radically polymerizable or crosslinkable compounds known in the industry can be used.
  • polyfunctional vinyl ether can be mentioned.
  • the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butylene glycol divinyl ether, butanediol divinyl ether, Divinyl ethers such as hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetrabi Ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pen
  • radical polymerizable compound examples include, for example, JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, JP-T-2004.
  • Photo-curable polymerizable compounds used in the photopolymerizable compositions described in each publication such as 5114014 are known, and these can also be applied to the ink composition of the present invention.
  • the molecular weight of the polyfunctional polymerizable compound is preferably 130 to 3000, and more preferably 130 to 500, as the molecular weight.
  • the content of the polyfunctional polymerizable compound in the total polymerizable compound is preferably 0.1 to 20% by mass. Is more preferably from 10 to 10% by weight, particularly preferably from 1 to 5% by weight.
  • the ink composition according to the first and second aspects of the present invention contains a polymerization initiator.
  • the polymerization initiator of the present invention may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferably mentioned.
  • the photopolymerization initiator a known photopolymerization initiator can be appropriately selected and used according to the kind of the polymerizable compound and the purpose of use of the ink composition.
  • the photopolymerization initiator used in the ink composition of the present invention is a compound that absorbs external energy (light) and generates radicals that are polymerization initiation species.
  • the light for initiating polymerization indicates active energy rays (active irradiation rays), that is, ⁇ rays, ⁇ rays, electron beams, ultraviolet rays, visible rays, infrared rays, etc., preferably ultraviolet rays. .
  • photopolymerization initiator known compounds can be used.
  • Preferred photopolymerization initiators that can be used in the present invention include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, Examples include thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
  • ⁇ -aminoketone is also mentioned as a preferable photopolymerization initiator that can be used in the present invention.
  • these photopolymerization initiators may be used alone or in combination.
  • the photopolymerization initiator in the present invention is preferably used alone or in combination of two or more.
  • aromatic ketones examples include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY”, J. Am. P. FOUASSIER, J.A. F. RABEK (1993), pp. And compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117.
  • More preferred examples include ⁇ -thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, ⁇ -substituted benzoin compounds described in JP-B-47-22326, Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, Benzoin ethers described in JP-A No. 62-81345, Japanese Patent Publication No. 1-334242, US Pat. No. 4,318,791, ⁇ -aminobenzophenones described in European Patent No.
  • aromatic ketones or acylphosphine oxide compounds are preferably used as photopolymerization initiators, and p-phenylbenzophenone (manufactured by Wako Pure Chemical Industries, Ltd.), bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide (Irgacure 819: manufactured by BASF Japan), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phos Fin oxides (Darocur TPO: BASF Japan Ltd., Lucirin TPO: BASF Japan Ltd.) are preferred.
  • Irg907 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF Japan Ltd.).
  • a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the polymerization initiator in the ink composition of the first aspect of the present invention is preferably 1 to 25% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 15%, based on the ink composition. % By mass.
  • the content of the polymerization initiator in the ink composition according to the second aspect of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably based on the ink composition. Is 1 to 10% by mass.
  • the ink composition according to the first aspect of the present invention may contain a colorant.
  • the ink composition according to the second aspect of the present invention contains a colorant.
  • a colorant By adding a colorant to the ink composition, the ink composition can form a visible image (colored image).
  • the colorant that can be used in the ink composition of the present invention is not particularly limited, and various known colorants (pigments and dyes) can be appropriately selected and used depending on the application. For example, when forming an image excellent in weather resistance, a pigment is preferable.
  • the dye both water-soluble dyes and oil-soluble dyes can be used, but oil-soluble dyes are preferred.
  • the pigment that is preferably used as the colorant in the ink composition in the first and second aspects of the present invention will be described.
  • the pigment is not particularly limited, and is obtained by dispersing all commercially available organic pigments and inorganic pigments in an insoluble resin or the like as a dispersion medium, or by grafting a resin on the pigment surface. Etc. can be used. Moreover, what dye
  • organic pigments and inorganic pigments that can be used in the present invention include, for example, C.I. I. Pigment Yellow 1 (Fast Yellow G, etc.), C.I. I. A monoazo pigment such as C.I. Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow AAA, etc.), C.I. I. Disazo pigments such as C.I. Pigment Yellow 17; I. Non-benzidine type azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.); I.
  • Acidic dye lake pigments such as C.I. Pigment Yellow 115 (such as quinoline yellow lake);
  • Basic dye lake pigments such as CI Pigment Yellow 18 (Thioflavin Lake, etc.), anthraquinone pigments such as Flavantron Yellow (Y-24), isoindolinone pigments such as Isoindolinone Yellow 3RLT (Y-110), and quinophthalone yellow Quinophthalone pigments such as (Y-138), isoindoline pigments such as isoindoline yellow (Y-139), C.I.
  • Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.);
  • I. And metal complex salt azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.).
  • Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I.
  • Azo lake pigments such as C.I. Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I.
  • Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as C.I. Pigment Red 149 (perylene scarlet, etc.); I. Pigment violet 19 (unsubstituted quinacridone), C.I. I.
  • Quinacridone pigments such as CI Pigment Red 122 (quinacridone magenta, etc.); I. Isoindolinone pigments such as CI Pigment Red 180 (isoindolinone red 2BLT, etc.); I. And alizarin lake pigments such as CI Pigment Red 83 (Mada Lake, etc.).
  • C.I. I. Disazo pigments such as C.I. Pigment Blue 25 (Dianisidine Blue, etc.); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (Peacock Blue Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (Viclotia Pure Blue BO Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkali blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1).
  • C.I. I. Pigment green 7 phthalocyanine green
  • C.I. I. Phthalocyanine pigments such as C.I. Pigment Green 36 (phthalocyanine green)
  • I. And azo metal complex pigments such as CI Pigment Green 8 (Nitroso Green).
  • An isoindoline pigment such as C.I. Pigment Orange 66 (isoindoline orange); I. And anthraquinone pigments such as CI Pigment Orange 51 (dichloropyrantron orange).
  • black pigments examples include carbon black, titanium black, and aniline black.
  • the white pigment examples include basic lead carbonate (2PbCO 3 Pb (OH) 2 , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO 2 , so-called titanium white), Strontium titanate (SrTiO 3 , so-called titanium strontium white) or the like can be used.
  • a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used.
  • a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used.
  • a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a k
  • a dispersant when dispersing the pigment.
  • the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a high molecular weight unsaturated acid ester, a high molecular weight copolymer, a modified polyacrylate, an aliphatic polyacrylate.
  • a commercially available polymer dispersant such as Solsperse series manufactured by Lubrizol.
  • a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
  • the ink composition as a dispersion medium for various components such as pigments, a solvent may be added, the polymerizable compound which is a low molecular weight component may be used as a dispersion medium, and a low molecular weight without a solvent.
  • the polymerizable compound as a component may be used as a dispersion medium, but the ink composition of the present invention is suitable as an active energy ray-curable ink, and is cured after being applied to a recording medium. It is preferable that there is no solvent. The definition of the active energy ray will be described later.
  • the volume average particle diameter of the pigment particles in the ink composition is preferably 0.02 ⁇ m to 0.60 ⁇ m, more preferably 0.02 ⁇ m to 0.10 ⁇ m. Further, the maximum particle size is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less, and the selection of the pigment, dispersant, dispersion medium, dispersion conditions, and filtration conditions are set so as to be in such a range.
  • the volume average particle diameter is measured using a laser diffraction / scattering particle size distribution analyzer (LA920, manufactured by Horiba, Ltd.) using tripropylene glycol methyl ether as a measurement solvent.
  • the dye can be appropriately selected from conventionally known compounds (dyes). Specific examples include compounds described in paragraph numbers [0023] to [0089] of JP-A No. 2002-114930 and paragraph numbers [0136] to [0140] of JP-A No. 2008-13646. These can also be applied to the present invention.
  • the colorant is preferably added in the ink composition in an amount of 0.05% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass with respect to the total mass of the ink composition.
  • the content is particularly preferably 0.2% by mass to 6% by mass with respect to the total mass (including the solvent) of the ink composition.
  • the ink composition of the present invention is preferably a non-aqueous ink composition containing substantially no water. Specifically, it is preferably 3% by mass or less, more preferably 2% by mass or less, and most preferably 1% by mass or less with respect to the total amount of the ink composition.
  • the ink composition of the present invention may further contain a chain transfer agent.
  • the chain transfer agent can be used without particular limitation as long as it is a substance that moves the active site of the reaction by a chain transfer reaction in the polymerization reaction.
  • chain transfer agent examples include, for example, halogen compounds such as carbon tetrachloride and carbon tetrabromide; alcohols such as isopropyl alcohol and isobutyl alcohol; 2-methyl-1-butene, 2,4 -Olefins such as -diphenyl-4-methyl-1-pentene; sulfur-containing compounds; and the like, but are not limited thereto.
  • halogen compounds such as carbon tetrachloride and carbon tetrabromide
  • alcohols such as isopropyl alcohol and isobutyl alcohol
  • 2-methyl-1-butene, 2,4 -Olefins such as -diphenyl-4-methyl-1-pentene
  • sulfur-containing compounds and the like, but are not limited thereto.
  • the molecular weight of the chain transfer agent is preferably 250 or more, particularly preferably 250 or more and 100,000 or less, more preferably 500 or more and 80,000 or less, and particularly preferably 3,000 or more and 80,000 or less. Only 1 type may be used for a chain transfer agent and it may use 2 or more types together.
  • the addition amount of the chain transfer agent to the ink composition of the second aspect of the present invention is 0.1% by mass to 15% by mass with respect to the total solid mass of the ink composition. %, More preferably 0.5% by mass to 10% by mass, and particularly preferably 1% by mass to 10% by mass.
  • sensitizing dye A sensitizing dye can be added to the ink composition of the present invention in order to promote decomposition of the polymerization initiator by irradiation with active energy rays.
  • the sensitizing dye a compound corresponding to the wavelength of the active energy ray that generates an initiation species in the polymerization initiator used in the ink composition may be used, but it is used for a curing reaction of a general ink composition.
  • preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
  • Polynuclear aromatics for example, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, isopropylthioxanthone
  • xanthenes for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • cyanines for example, thiaxene
  • merocyanines eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue, toluidine blue
  • acridines eg, acridine orange, chloroflavin, acriflavine
  • anthraquinones examples include anthraquinone), squalium (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin), polyn
  • Xanthones may be mentioned as preferred class.
  • DETX 2,4-diethylthioxanthone, Sun Chemical Co., Ltd.
  • ITX 2-isopropylthioxanthone, Tokyo Kasei Kogyo Co., Ltd.
  • sensitizing dyes described in JP-A-2008-95086 are also suitable.
  • the ink composition of the present invention can also contain a co-sensitizer.
  • co-sensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Science”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
  • co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, ⁇ -mercapto. And naphthalene.
  • thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, ⁇ -mercapto. And naphthalene.
  • co-sensitizers include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- 34414, a hydrogen donor described in JP-A-6-308727, a sulfur compound (eg, trithiane), a phosphorus compound described in JP-A-6-250387 (diethylphosphite, etc.), and JP-A-8-65779. And Si—H and Ge—H compounds described in the above No.
  • UV absorber An ultraviolet absorber can be used in the ink composition of the present invention. Examples of the ultraviolet absorber are described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-197075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No.
  • JP-B-48-30492 JP-A-56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP
  • antioxidant can be added to the ink composition of the present invention.
  • examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. No. 54, JP-A-54-48535, JP-A-62-262047, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
  • organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and the like.
  • metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, Vi, I to J, no. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid.
  • the compounds described in the patent cited in Japanese Patent No. 15162 and the compounds included in the formulas and compound examples of the representative compounds described in JP-A-62-215272, pages 127 to 137 can be used.
  • Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition of the present invention.
  • the conductive salts may be added for the purpose of controlling ejection physical properties.
  • the ink composition of the present invention preferably contains no solvent, but may contain a very small amount of a non-curable organic solvent. Specifically, it is preferably 2% by mass or less, and more preferably 1% by mass or less, with respect to the ink composition.
  • the content of the solvent of the ink composition in the second aspect of the present invention is preferably 1% by mass or less based on the total amount of the ink composition.
  • the solvent examples include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride.
  • ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone
  • alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol
  • chlorine such as chloroform and methylene chloride.
  • Solvents aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
  • oil-soluble polymer compounds can be added to the ink composition of the present invention.
  • the various oil-soluble polymer compounds may be used for adjusting film physical properties.
  • oil-soluble polymer compounds include acrylic copolymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, Acrylic resins, rubber resins, waxes, and other natural resins can be used. Two or more of these may be used in combination.
  • a polymer compound that easily segregates on the surface for the purpose of improving tackiness or the like is also suitable.
  • These polymer compounds contain Si and F atoms described in paragraph numbers [0017] to [0037] of JP-A-2008-248119, paragraph numbers [0015] to [0034] of JP-A-2005-250890, and the like.
  • a polymer, a polymer having a long-chain alkyl group in the side chain, and the like can be used.
  • a surfactant may be added to the ink composition of the present invention.
  • the surfactant include those described in JP-A Nos. 62-173463 and 62-183457.
  • anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks
  • Nonionic surfactants such as copolymers
  • cationic surfactants such as alkylamine salts and quaternary ammonium salts.
  • An organic fluoro compound may be used in place of the surfactant.
  • the organic fluoro compound is preferably hydrophobic.
  • Examples of the organic fluoro compound include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). (Columns 8 to 17) and those described in JP-A Nos. 62-135826. (Preferred physical properties of ink composition)
  • the ink composition of the present invention is suitably used for inkjet recording applications. For this reason, the viscosity at the temperature at the time of discharge (for example, 40 ° C. to 80 ° C., preferably 25 ° C. to 30 ° C.) in consideration of discharge properties. Is preferably 7 mPa ⁇ s to 30 mPa ⁇ s. More preferably, it is 7 mPa ⁇ s to 20 mPa ⁇ s.
  • the ink composition of the present invention preferably has a surface tension at 25 ° C. of 20 to 40 mN / m.
  • the surface tension is measured at 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • the ink composition in the second embodiment it is preferable to use an ink composition having a viscosity at 25 ° C. of 40 mPa ⁇ s or less. More preferably, it is 5 to 40 mPa ⁇ s, and further preferably 7 to 30 mPa ⁇ s.
  • the viscosity at the discharge temperature preferably 25 to 80 ° C., more preferably 25 to 50 ° C.
  • the viscosity at the discharge temperature is preferably 3 to 15 mPa ⁇ s, and preferably 3 to 13 mPa ⁇ s. Is more preferable.
  • the ink composition in the second aspect of the present invention is preferably adjusted in composition ratio as appropriate so that the viscosity is in the above range.
  • the viscosity is measured under the condition of 25 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYOCO.LTD).
  • the surface tension of the ink composition according to the second aspect of the present invention at 25 ° C. is preferably 20 to 35 mN / m, and more preferably 23 to 33 mN / m.
  • 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and 35 mN / m or less is preferable in terms of wettability.
  • the surface tension is measured at 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • the ink composition of the present invention is suitably used for inkjet recording.
  • the ink composition of the present invention When applied to ink jet recording, the ink composition of the present invention is ejected onto a recording medium by an ink jet recording apparatus, and then the ejected ink composition is irradiated with an energy ray and cured to perform recording.
  • the ink composition according to the first aspect of the present invention includes (Component A) a polymer having a group containing a silsesquioxane structure and a weight average molecular weight of 3,000 or more, (Component B) a monofunctional polymerizable compound, and (Component). C) It has been found that the effect of the present invention is improved by having a polymerization initiator. Although this mechanism is not sufficiently clarified, the present inventors speculate as follows. That is, (Component A) is dispersed in the polymerizable compound in the ink and takes a phase separation structure (sea-island structure) when the ink composition is cured. ) Can be suppressed, and it is surmised that the punching characteristics are improved.
  • the present inventors have (Component A ′) a compound having no ethylenically unsaturated double bond and having a silsesquioxane structure and having a molecular weight of 300 to less than 3000, (Component B ′) a monofunctional polymerizable compound, (Component C) A polymerization initiator and (Component D) a colorant, and the content of (Component B ′) monofunctional polymerizable compound relative to the total content of all polymerizable compounds is 80% by mass or more,
  • the effect of the present invention is improved. Although it is not clear about this mechanism, the present inventors speculate as follows.
  • the image forming method according to the first aspect of the present invention includes an ink application step of applying the ink composition of the present invention onto a recording medium, and a step of irradiating the applied ink composition with active energy rays. ,including. Furthermore, you may have the process of obtaining the printed matter which has the image hardened
  • the ink application step is used for various printing applications such as lithographic printing applications and screen printing applications, and it is preferable that an image is formed by ejecting ink by an ink jet method including a commercially available apparatus.
  • the image forming method includes an ink application step of applying the ink composition of the present invention onto a recording medium, and an irradiation step of irradiating the ink composition with active energy rays.
  • an image is preferably formed by ejecting ink by an ink jet method including a commercially available apparatus.
  • the ink application process can be used for various printing applications such as lithographic printing applications and screen printing applications.
  • the image forming method may include a step of obtaining a printed matter having a cured image on the recording medium.
  • the recording medium (base material) that can be applied to the image forming method of the present invention is not particularly limited, and various non-absorbent resin materials used for ordinary non-coated paper, coated paper, and other so-called soft packaging or Resin film formed into a film can be used, and various plastic films include, for example, PET film, OPS film, OPP film, ONy film, PVC film, PE film, TAC film, vinyl chloride sheet, soft A vinyl chloride sheet etc. can be mentioned.
  • examples of the plastic that can be used as the recording medium material include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. Metals and glasses can also be used as a recording medium.
  • examples of the recording medium applicable to the present invention include a lithographic printing plate support.
  • Examples of active energy rays applied to the image forming method of the present invention include ⁇ rays, ⁇ rays, X rays, ultraviolet rays, visible rays, infrared rays, and electron beams.
  • the peak wavelength of the active energy ray is preferably 200 nm to 600 nm, more preferably 300 nm to 450 nm, and still more preferably 350 nm to 420 nm.
  • the output of the active energy rays is preferably 2,000 mW / cm 2 or less, more preferably at 10mW / cm 2 ⁇ 2,000mW / cm 2, more preferably, 20mW / cm 2 ⁇ 1 a 000mW / cm 2, particularly preferably 50mW / cm 2 ⁇ 800mW / cm 2.
  • the active energy ray irradiation, emission wavelength peak is 350 nm ⁇ 420 nm, and maximum illuminance of the recording medium surface is 10mW / cm 2 ⁇ 2,000mW / cm 2
  • the light is preferably emitted from a light emitting diode that generates ultraviolet rays.
  • the ink composition of the present invention can be cured with high sensitivity even with low exposure light such as light emitted from a light emitting diode.
  • the active energy rays can be exposed collectively after ejecting all colors, but it is preferable to expose each color.
  • the ink composition of the present invention is suitably used for image formation of general printed matter, and also suitable for a mode in which an image is formed on a recording medium such as a support and then processed. Can be used.
  • the printed matter molded body may be processed and molded using the printed matter formed by the image forming method of the present invention.
  • the printed product is formed by ejecting the ink composition of the present invention onto a recording medium by an inkjet method to form an image, and irradiating the obtained image with active energy rays to cure the ink composition. And producing a print product having a cured image on the recording medium and a process for obtaining a print product by molding the print product to obtain a print product.
  • a recording medium used for the production of the printed matter molded body a recording medium made of a moldable resin material is used, and examples thereof include PET, polycarbonate, polystyrene and the like.
  • vacuum forming As a processing method for producing a printed product, vacuum forming, pressure forming, or vacuum / pressure forming is most preferable.
  • the vacuum forming a flat support is preheated to a temperature at which heat deformation is possible in advance, and this is sucked into a mold by decompression and stretched by being compressed and cooled to the mold. Pressurization is performed from the opposite side and pressure-bonded cooling to the mold is performed.
  • vacuum / pressure forming the pressure reduction and pressurization are performed simultaneously.
  • pigment dispersions (Y1, M1, C1, K1, and W1) for each color.
  • Magenta pigment dispersion (M1) Pigment: C.I. I. Pigment Red 57: 1 15 parts
  • Dispersant Polymer dispersant [manufactured by Nippon Lubrizol Corporation, Solsperse 32000] 5 parts
  • Monofunctional monomer 2-phenoxyethyl acrylate 80 parts
  • MDI (4,4'-diphenylmethane diisocyanate, the following structure, manufactured by Sigma-Aldrich Japan)
  • H12MDI (dicyclohexylmethane diisocyanate, the following structure, manufactured by Sigma-Aldrich Japan)
  • TMHDI Trimethylhexamethylene Diisocyanate (2,2,4- and 2,4,4- mixture), manufactured by Tokyo Chemical Industry Co., Ltd.
  • DEG Diethylene glycol UM-90 (3/1): (ETERRNACOLL UM-90 (3/1): polycarbonate diol, cyclohexane dimethanol, 1,6-hexanediol (3: 1) base, manufactured by Ube Industries, Ltd.)
  • UH-50 (ETERNACOLL UH-50: polycarbonate diol, 1,6-hexanediol base, manufactured by Ube Industries, Ltd.)
  • PPG300 (polypropylene glycol diol, number average molecular weight 300, manufactured by Wako Pure Chemical Industries, Ltd.)
  • PPG700 (polypropylene glycol diol, number average molecular weight 700, manufactured by Wako Pure Chemical Industries, Ltd.)
  • PPG1000 (polypropylene glycol diol, number average molecular weight 1000, manufactured by Wako Pure Chemical Industries, Ltd.)
  • PLACCEL 205U (Polycaprolactone diol, number average molecular weight 530, manufactured
  • Example 1 ⁇ Preparation of ink composition> -Example 1- The following components were mixed to prepare the ink composition of Example 1.
  • Example 2 to 31 were carried out in the same manner as in Example 1 except that the pigment dispersion, polymerizable compound (monofunctional polymerizable compound and polyfunctional polymerizable compound) and (Component A) were changed as shown in the table below. And Comparative Examples 1 and 2 were prepared.
  • surface represents the following.
  • the prepared ink composition was filtered with a filter having an absolute filtration accuracy of 2 ⁇ m.
  • a recording medium soft vinyl chloride sheet, thickness 50 ⁇ m, AVERY
  • a piezo-type inkjet nozzle trade name LuxJet UV350GTW, manufactured by FUJIFILM Corporation.
  • the ink supply system consists of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head.
  • the ink supply tank is insulated and heated from the inkjet head part, and the nozzle part is always 45 ° C.
  • the temperature was controlled so as to be ⁇ 2 ° C.
  • the piezo-type inkjet head was driven so that multi-size dots of 8 pl to 30 pl could be ejected at a resolution of 600 ⁇ 450 dpi (dot per inch) to form a solid image. Note that dpi (dot per inch) in the present invention represents the number of dots per 2.54 cm.
  • the prepared ink composition was stored at 75% RH and 60 ° C. for 3 days, and then allowed to cool to a discharge temperature (45 ° C. ⁇ 2 ° C.). Subsequently, the ink viscosity at a temperature of 45 ° C. ⁇ 2 ° C. was measured, and the increase in the ink viscosity was calculated by the viscosity ratio after storage / before storage.
  • the ink compositions of the examples all had a change in viscosity of 1.3 or less, and the storage stability was good.
  • the blocking sensitivity is a UV-irradiation using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having a high-pressure mercury lamp. (Exposure) to cure the image and obtain a print. Using an image formed by increasing the exposure energy in increments of 1000 mJ / cm 2 , it was confirmed how much exposure energy caused blocking. Specifically, 500 sheets of recording medium (soft vinyl chloride sheet) on which no image was formed were placed on each of the images formed after UV irradiation and left for a day. Furthermore, the transfer onto the superimposed recording medium was visually evaluated.
  • the case where transfer could not be easily confirmed was regarded as a pass line
  • the case where transfer could be easily confirmed was regarded as a fail line
  • the exposure energy amount [mJ / cm 2 ] required to reach the pass line was defined as blocking sensitivity.
  • the allowable range of blocking sensitivity is 12,000 mJ / cm 2 or less, and preferably 6,000 mJ / cm 2 or less.
  • the recording medium soft vinyl chloride sheet
  • FassonPE polyethylene film manufactured by Fasson Co., Ltd., film thickness: 100 ⁇ m
  • a printed material for evaluation of stretchability was obtained in the same manner except that ultraviolet irradiation was performed in place of cm 2 and illuminance: 2,140 mW / cm 2 .
  • the obtained printed material for evaluation of stretchability is cut into an axial length of 5 cm and a width of 2.5 cm, and stretched at a speed of 30 cm / min using a tensile tester (manufactured by Shimadzu Corporation), whereby the cured film breaks. The rate was measured.
  • the state of elongation from the initial length to twice the length was defined as 100% elongation.
  • the allowable range of the stretching ratio is 200% or more, and preferably 300% or more.
  • a vacuum forming apparatus forming 300X [manufactured by Seiko Sangyo Co., Ltd.] a polycarbonate sheet (manufactured by Teijin Kasei Co., Ltd.) was used instead of a recording medium for evaluating the stretch ratio.
  • the wooden mold shown in FIG. 1 was installed in the center of the vacuum table of the vacuum forming apparatus, and the heater temperature was set so that the temperature of the recording medium as a support was 170 ° C. After the temperature of the recording medium was heated to 170 ° C., the vacuum table on which the wooden mold was installed was slowly raised while operating with a table lifting lever, and vacuum forming was performed. The molded printed matter was visually observed for cracks and white spots, and evaluated according to the following evaluation criteria.
  • -Evaluation criteria- A The occurrence of cracks or white spots could not be confirmed.
  • B The occurrence of cracks or white spots was slightly confirmed.
  • -Evaluation criteria- A Almost no cracking occurred in the periphery of the hole even when confirmed by an optical microscope.
  • B Fine cracks that could not be visually confirmed around the hole occurred.
  • C A crack that can be visually confirmed was generated around the hole.
  • the ink composition of the example according to the first aspect of the present invention can obtain a printed material having both good moldability and punching characteristics as compared with the ink composition of the comparative example. it can. Furthermore, the ink composition according to the first aspect of the present invention has good ink storage stability, ejection stability, and blocking sensitivity.
  • pigment dispersions (Y2, M2, C2, K2 and W2) for each color.
  • the pigment dispersion was prepared in a disperser Motor Mill M50 (manufactured by Eiger) and dispersed using a zirconia bead having a diameter of 0.65 mm at a peripheral speed of 9 m / s for the time shown in the table below.
  • Example 32 The following ingredients were stirred with a Silverson rotor / stator type high shear mixer to prepare an ink composition of Example 32.
  • Magenta Pigment Dispersion (M2) 13 parts (A-1-1) (Trade Name Isooctyl POSS Cage Mixture, MS0805, (Component A ′), Hybrid Plastic Co., Ltd.), 0.1 part NVC (( Component B ') Monofunctional polymerizable compound, N-vinylcaprolactam) 33 parts FA513AS ((Component B') monofunctional polymerizable compound, dicyclopentanyl acrylate) 23.9 parts NIPAM ((Component B ') single Functional polymerizable compound, N-isopropylacrylamide, Tokyo Chemical Industry Co., Ltd.) 20 parts HDDA (polyfunctional polymerizable compound, 1,6-hexanediol diacrylate) 1 part Irg819 (BASF Japan Ltd., (Component C ) Polymerization initiator
  • Example 33 to Example 65 Comparative Example 3 to Comparative Example 4- Except for changing the pigment dispersion, the polymerizable compound (monofunctional polymerizable compound and polyfunctional polymerizable compound), and (Component A ′) as shown in Table 22 and Table 23, the same as in Example 32, Examples 33 to 65 and Comparative Examples 3 to 4 were prepared. Abbreviations in the table represent the following.
  • the prepared ink composition was filtered with a filter having an absolute filtration accuracy of 2 ⁇ m.
  • an image was formed on a recording medium using an inkjet recording experimental apparatus having a piezo-type inkjet nozzle (trade name LuxJet UV350GTW, manufactured by FUJIFILM Corporation).
  • the ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion.
  • Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ⁇ 2 ° C.
  • the piezo-type inkjet head was driven so that multi-size dots of 8 to 30 pl could be ejected at a resolution of 720 ⁇ 720 dpi to form a solid image.
  • UV light was condensed to an exposure surface illuminance of 2,100 mW / cm 2 , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium.
  • the integrated light amount irradiated to the image was set to 3,000 mJ / cm 2 .
  • a HAN250NL high-cure mercury lamp manufactured by GS Yuasa Corporation was used as the ultraviolet lamp.
  • dpi represents the number of dots per 2.54 cm.
  • Panlite PC-1151 film thickness 500 ⁇ m, polycarbonate sheet, manufactured by Teijin Chemicals Ltd. was used. Each sample was drawn so that the average film thickness of the cured film of the ink composition was 12 ⁇ m.
  • a printed material was produced by the same method as the image forming method described above. Under the condition of 25 ° C., the printed material produced was punched with a large punch for manual OA No. Drilling was performed using 200N (manufactured by Lion Corporation). The image was observed with a 100 ⁇ optical microscope for cracks around the perforated portion of the image, and visually observed for light transmission. 4: Cracks around punch holes and no light transmission. 3: There was a crack around the punch hole, but no light was transmitted. 2: There were cracks and light transmission around the punch hole, but the level was satisfactory. 1: Cracks were generated around the punch hole and light was transmitted, which was unsuitable as a product.
  • the indentation method was used.
  • a Fischer Instruments HM-500 manufactured by Fischer Instruments was used as the apparatus, the indenter was Belkovic (triangular pyramid with a tip opening angle of 144 ° 34 ′), the load was 0.05 mN, and the indentation depth was 0.3 ⁇ m.
  • the film hardness was determined from the load at the time of pressing and the contact area between the sample and the indenter. The hardness is preferably 80 N / mm 2 or more.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une composition d'encre qui contient : un polymère qui présente un groupe contenant une structure de silsesquioxane et présente une masse moléculaire moyenne en poids de 3 000 ou plus (composant A) ; un composé polymérisable monofonctionnel (composant B) ; et un amorceur de polymérisation (composant C). L'invention concerne également une autre composition d'encre qui contient : un composé qui n'a pas de double liaison d'insaturation éthylénique mais qui présente une structure de silsesquioxane, tout en ayant une masse moléculaire de 300 ou plus mais inférieure à 3 000 (composant A') ; un composé polymérisable monofonctionnel (composant B') ; un amorceur de polymérisation (composant C) ; et un agent colorant (composant D). La teneur du composé polymérisable monofonctionnel (composant B') par rapport à la teneur totale de tous les composés polymérisables est de 80 % en masse ou plus.
PCT/JP2012/054449 2011-02-28 2012-02-23 Composition d'encre, procédé de formation d'image et matière imprimée WO2012117944A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12752941.0A EP2682438B1 (fr) 2011-02-28 2012-02-23 Composition d'encre et procédé de formation d'image
CN2012800101976A CN103391979A (zh) 2011-02-28 2012-02-23 油墨组合物、图像形成方法及印相物
EP16188910.0A EP3124557B1 (fr) 2011-02-28 2012-02-23 Composition d'encre et procédé de formation d'image
US14/010,300 US10407582B2 (en) 2011-02-28 2013-08-26 Ink composition, image forming method, and printed matter

Applications Claiming Priority (4)

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JP2011041819A JP5819616B2 (ja) 2011-02-28 2011-02-28 インク組成物、画像形成方法及び印画物
JP2011-042199 2011-02-28
JP2011-041819 2011-02-28
JP2011042199A JP2012180389A (ja) 2011-02-28 2011-02-28 インク組成物、画像形成方法及び印画物

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WO2017104318A1 (fr) * 2015-12-18 2017-06-22 富士フイルム株式会社 Composition liquide pour imprimante jet d'encre

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JP6027971B2 (ja) * 2011-08-23 2016-11-16 サカタインクス株式会社 光硬化型インクジェット印刷用インク組成物、印刷物、及び、成形加工品
US9683119B2 (en) 2014-07-03 2017-06-20 Corning Incorporated Jet ink composition, method and coated article
JP6412824B2 (ja) * 2015-05-01 2018-10-24 富士フイルム株式会社 レンチキュラー印刷物の製造方法
JP6547674B2 (ja) * 2015-05-15 2019-07-24 信越化学工業株式会社 光硬化性組成物及びこれを含む硬化物
JP6977467B2 (ja) * 2017-10-13 2021-12-08 富士フイルムビジネスイノベーション株式会社 三次元造形物及び三次元造形物の製造方法
JP2020117586A (ja) * 2019-01-22 2020-08-06 株式会社リコー 硬化型組成物、収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、及び硬化物
CN110018142B (zh) * 2019-03-20 2021-10-22 西南交通大学 复合荧光基底、复合荧光基底的制备方法以及应用
CN114015277B (zh) * 2021-10-19 2023-05-12 杭州福斯特电子材料有限公司 一种用于oled封装的油墨组合物及其应用

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CN103391979A (zh) 2013-11-13
EP2682438A1 (fr) 2014-01-08
US20140066538A1 (en) 2014-03-06
EP2682438B1 (fr) 2017-04-05
EP3124557B1 (fr) 2018-08-22
EP3124557A1 (fr) 2017-02-01

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